Ammonia slip catalyst with in-situ pt fixing

ABSTRACT

The invention relates to a catalytic article comprising a substrate having an inlet and an outlet; a first coating comprising a blend of: (1) platinum on a support, and (2) a first SCR catalyst comprising a Cu- and Mn-exchanged molecular sieve; and a second coating comprising a second SCR catalyst; wherein the support comprises at least one of a zeolite or a SiO 2 -Al 2 O 3  mixed oxide. The platinum may be fixed on the support in solution.

BACKGROUND OF THE INVENTION

Hydrocarbon combustion in diesel engines, stationary gas turbines, andother systems generates exhaust gas that must be treated to removenitrogen oxides (NOx), which comprises NO (nitric oxide) and NO₂(nitrogen dioxide), with NO being the majority of the NOx formed. NOx isknown to cause a number of health issues in people as well as causing anumber of detrimental environmental effects including the formation ofsmog and acid rain. To mitigate both the human and environmental impactfrom NO, in exhaust gas, it is desirable to eliminate these undesirablecomponents, preferably by a process that does not generate other noxiousor toxic substances.

Exhaust gas generated in lean-burn and diesel engines is generallyoxidative. NOx needs to be reduced selectively with a catalyst and areductant in a process known as selective catalytic reduction (SCR) thatconverts NOx into elemental nitrogen (N₂) and water. In an SCR process,a gaseous reductant, typically anhydrous ammonia, aqueous ammonia, orurea, is added to an exhaust gas stream prior to the exhaust gascontacting the catalyst. The reductant is absorbed onto the catalyst andthe NO_(x) is reduced as the gases pass through or over the catalyzedsubstrate. In order to maximize the conversion of NOx, it is oftennecessary to add more than a stoichiometric amount of ammonia to the gasstream. However, release of the excess ammonia into the atmosphere wouldbe detrimental to the health of people and to the environment. Inaddition, ammonia is caustic, especially in its aqueous form.Condensation of ammonia and water in regions of the exhaust linedownstream of the exhaust catalysts can result in a corrosive mixturethat can damage the exhaust system. Therefore, the release of ammonia inexhaust gas should be eliminated. In many conventional exhaust systems,an ammonia oxidation catalyst (also known as an ammonia slip catalyst or“ASC”) is installed downstream of the SCR catalyst to remove ammoniafrom the exhaust gas by converting it to nitrogen. The use of ammoniaslip catalysts can allow for NO, conversions of greater than 90% over atypical diesel driving cycle.

It would be desirable to have a catalyst that provides for both NOxremoval by SCR and for selective ammonia conversion to nitrogen, whereammonia conversion occurs over a wide range of temperatures in avehicle's driving cycle, and minimal nitrogen oxide and nitrous oxidebyproducts are formed.

SUMMARY OF THE INVENTION

According to some embodiments of the present invention, a catalyticarticle may include: a substrate having an inlet and an outlet; a firstcoating comprising a blend of: (1) platinum on a support, and (2) afirst SCR catalyst comprising a Cu- and Mn-exchanged molecular sieve;and a second coating comprising a second SCR catalyst; wherein thesupport comprises at least one of a molecular sieve or a SiO₂-Al₂O₃mixed oxide. In some embodiments, the platinum is fixed on the supportin solution.

In some aspects, the first SCR catalyst molecular sieve comprises asmall pore molecular sieve, such as AEI, CHA, or combinations thereof.In some aspects, the first SCR catalyst molecular sieve is essentiallyfree of any transition metals beyond the Cu and Mn. In some aspects, thefirst SCR catalyst molecular sieve contains additional transition metalsin an amount less than about 1 wt %. In some aspects, the first SCRcatalyst molecular sieve comprises Cu and Mn in a combined amount ofabout 0.10 to about 10% by weight of the Cu- and Mn-exchanged molecularsieve. The first SCR catalyst molecular sieve may include Cu in anamount of about 0.05 to about 5% by weight of the Cu- and Mn-exchangedmolecular sieve. The first SCR catalyst molecular sieve may include Mnin an amount of about 0.05 to about 5% by weight of the Cu- andMn-exchanged molecular sieve. In some aspects, the first SCR catalystmolecular sieve comprises Cu and Mn in a weight ratio of about 0.1 toabout 50.

In some embodiments, the support comprises a SiO₂-Al₂O₃ mixed oxide. Insome embodiments, SiO₂ is present in an amount of 1 wt % to about 70 wt%, or about 40 wt % to about 70 wt % of the mixed oxide.

In some embodiments, the support comprises a molecular sieve. A suitablemolecular sieve may have an external surface area of at least 50 m²/g;at least 70 m²/g; or at least 100 m²/g. In some embodiments, a suitablemolecular sieve has an average crystal size of less than about 1 μm;less than about 0.5 μm; or less than about 0.3 μm. In some embodiments,a suitable molecular sieve comprises a zeolite having asilica-to-alumina ratio of greater than 100; greater than 300; orgreater than 1000. In certain embodiments, a molecular sieve is selectedfrom the group of Framework Types consisting of ACO, AEI, AEN, AFN, AFT,AFX, ANA, APC, APD, ATT, CDO, CHA, DDR, DFT, EAB, EDI, EPI, ERI, GIS,GOO, IHW, ITE, ITW, LEV, KFI, MER, MON, NSI, OWE, PAU, PHI, RHO, RTH,SAT, SAV, SIV, THO, TSC, UEI, UFI, VNI, YUG, ZON, BEA, MFI and FER andmixtures and/or intergrowths thereof. In some embodiments, the molecularsieve is selected from the group of Framework Types consisting of CHA,LEV, AEI, AFX, ERI, SFW, KFI, DDR, ITE, BEA, MFI and FER.

In some embodiments, the second coating that completely overlaps thefirst coating. In some embodiments, the second coating partiallyoverlaps the first coating. In some embodiments, the second coatingextends from the inlet end toward the outlet end covering less than afull length of the substrate. In some embodiments, the first coatingextends from the outlet end towards the inlet end covering less than afull length of the substrate. In some embodiments, the second SCRcatalyst is located on the inlet side of the coating comprising theblend of platinum on a support with the first SCR catalyst. In someembodiments, the second SCR catalyst is located on the outlet side ofthe coating comprising the blend of platinum on a support with the firstSCR catalyst.

In some embodiments, the platinum is present in an amount of at leastone of: (a) 0.01-0.3 wt. %; (b) 0.03-0.2 wt. %; (c) 0.05-0.17 wt. %; and(d) 0.07-0.15 wt. %, inclusive, relative to the weight of the support ofplatinum+the weight of platinum+the weight of the first SCR catalyst inthe blend. A weight ratio of the first SCR catalyst to platinum on thesupport may be in the range of at least one of: (a) 0:1 to 300:1, (b)3:1 to 300:1, (c) 7:1 to 100:1; and (d) 10:1 to 50:1, inclusive, basedon the weight of these components.

In some embodiments, the blend further comprises at least one ofpalladium (Pd), gold (Au) silver (Ag), ruthenium (Ru) or rhodium (Rh).

In certain embodiments, the second SCR catalyst is a base metal, anoxide of a base metal, a molecular sieve, a metal exchanged molecularsieve, a mixed oxide or a mixture thereof. The base metal may beselected from the group consisting of vanadium (V), molybdenum (Mo) andtungsten (W), chromium (Cr), cerium (Ce), manganese (Mn), iron (Fe),cobalt (Co), nickel (Ni), and copper (Cu), and mixtures thereof. Suchsecond SCR catalyst may further include at least one base metalpromoter.

Where the second SCR catalyst is a molecular sieve or a metal exchangedmolecular sieve, the molecular sieve or the metal exchanged molecularsieve may be small pore, medium pore, large pore or a mixture thereof.In some embodiments, the second SCR catalyst comprises a molecular sieveselected from the group consisting of aluminosilicate molecular sieves,metal-substituted aluminosilicate molecular sieves, aluminophosphate(AlPO) molecular sieves, metal-substituted aluminophosphate (MeAlPO)molecular sieves, silico-aluminophosphate (SAPO) molecular sieves, andmetal substituted silico-aluminophosphate (MeAPSO) molecular sieves, andmixtures thereof. In some embodiments, the second SCR catalyst comprisesa small pore molecular sieve selected from the group of Framework Typesconsisting of ACO, AEI, AEN, AFN, AFT, AFX, ANA, APC, APD, ATT, CDO,CHA, DDR, DFT, EAB, EDI, EPI, ERI, GIS, GOO, IHW, ITE, ITW, LEV, KFI,MER, MON, NSI, OWE, PAU, PHI, RHO, RTH, SAT, SAV, SIV, THO, TSC, UEI,UFI, VNI, YUG, and ZON, and mixtures and/or intergrowths thereof. Insome embodiments, the second SCR catalyst comprises a small poremolecular sieve selected from the group of Framework Types consisting ofCHA, LEV, AEI, AFX, ERI, SFW, KFI, DDR and ITE. In some embodiments, thesecond SCR catalyst comprises a medium pore molecular sieve selectedfrom the group of Framework Types consisting of AEL, AFO, AHT, BOF, BOZ,CGF, CGS, CHI, DAC, EUO, FER, HEU, IMF, ITH, ITR, JRY, JSR, JST, LAU,LOV, MEL, MFI, MFS, MRE, MTT, MVY, MWW, NAB, NAT, NES, OBW, -PAR, PCR,PON, PUN, RRO, RSN, SFF, SFG, STF, STI, STT, STW, SVR, SZR, TER, TON,TUN, UOS, VSV, WEI, and WEN, and mixtures and/or intergrowths thereof.In some embodiments, the second SCR catalyst comprises a large poremolecular sieve selected from the group of Framework Types consisting ofAFI, AFR, AFS, AFY, ASV, ATO, ATS, BEA, BEC, BOG, BPH, BSV, CAN, CON,CZP, DFO, EMT, EON, EZT, FAU, GME, GON, IFR, ISV, ITG, IWR, IWS, IWV,IWW, JSR, LTF, LTL, MAZ, MEI, MOR, MOZ, MSE, MTW, NPO, OFF, OKO, OSI,RON, RWY, SAF, SAO, SBE, SBS, SBT, SEW, SFE, SFO, SFS, SFV, SOF, SOS,STO, SSF, SSY, USI, UWY, and VET, and mixtures and/or intergrowthsthereof. In certain embodiments, the second SCR catalyst comprisespromoted-Ce—Zr or promoted-MnO₂.

A suitable substrate may include cordierite, a high porosity cordierite,a metallic substrate, an extruded SCR, a filter, or an SCRF.

According to some embodiments of the present invention, an exhaustsystem includes a catalytic article as described herein and a means forintroducing a reductant upstream of the catalytic article. An exhaustsystem may further include a third SCR catalyst that provides ≤100% NOxconversion, wherein the third SCR catalyst is a Cu-zeolite SCR catalystand is placed an exhaust gas flow upstream of the catalytic articledescribed herein.

According to some embodiments of the present invention, a method ofimproving NH₃ conversion an exhaust gas at a temperature of about 300°C. or less includes contacting an exhaust gas comprising ammonia with acatalytic article as described herein.

According to some embodiments of the present invention, a method ofimproving NH₃ conversion an exhaust gas at a temperature of about 300°C. or less includes contacting an exhaust gas comprising ammonia with acatalytic article as described herein, which has platinum which wasfixed on the support in solution. In some embodiments, NH₃ conversion isabout 30% to about 100% greater as compared to a catalyst comprising acomparable formulation in which the platinum is pre-fixed on thesupport.

According to some embodiments of the present invention, a method oftreating exhaust gas comprising ammonia and NOx includes contacting anexhaust gas comprising ammonia with a catalytic article as describedherein. In some embodiments, the weight ratio of ammonia to NOx in theexhaust gas is >1.0 for at least a portion of the operating time of thesystem.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1-8 are schematic representations of configurations of catalystscomprising a blend of (1) platinum on a support and (2) a first SCRcatalyst. The portion of the catalyst comprising a blend of (1) platinumon a support and (2) a first SCR catalyst, is labeled as “blend” inthese FIGS.

FIG. 1 depicts a configuration in which the second SCR catalyst ispositioned in the exhaust gas flow over the blend and the second SCRcovers the entire blend.

FIG. 2 depicts a configuration in which the second SCR catalyst ispositioned in the exhaust gas flow before the blend and the second SCRcovers the entire blend.

FIG. 3 depicts a configuration in which the second SCR catalyst ispositioned in the exhaust gas flow before the blend and the second SCRcovers a portion of, but not the entire blend.

FIG. 4 depicts a configuration in which the second SCR catalyst ispositioned in the exhaust gas flow before the blend and does not coverthe blend.

FIG. 5 depicts a configuration in which the second SCR catalyst coversthe entire blend and a portion of the second SCR is positioned in theexhaust gas flow after the blend.

FIG. 6 depicts a configuration in which the second SCR catalyst covers aportion of, but not the entire blend and a portion of the second SCR ispositioned in the exhaust gas flow after the blend.

FIG. 7 depicts a configuration in which a third SCR catalyst is a bottomlayer on a substrate, with a second layer comprising the blend,partially covering the third SCR catalyst, and a third layer, comprisinga second SCR catalyst, positioned over and covering all of the blendlayer.

FIG. 8 depicts a configuration in which a third SCR catalyst is a bottomlayer on a substrate, with a second layer comprising the blend,partially, but not completely, covering the third SCR catalyst, and athird layer, comprising a second SCR catalyst, positioned over andpartially, but not completely, covering the blend layer.

FIG. 9 shows the NH₃ slip, N₂O and NOx formation when various ASCs areexposed to one minute pulse of 1000 ppm NH₃.

FIG. 10 shows transient NH₃ oxidation performance of various ASCs.

DETAILED DESCRIPTION OF THE INVENTION

Catalysts of the present invention relate to ammonia slip catalystswhich may provide improved NH₃ conversion at lower temperatures, andwhich may be prepared more cost effectively. Catalyst articles ofembodiments of the present invention include a substrate with a firstcoating having a blend of: (1) platinum on a support, and (2) a firstSCR catalyst comprising a Cu- and Mn-exchanged molecular sieve, wherethe support includes a zeolite and/or a SiO₂-Al₂O₃ mixed oxide. Thecatalyst articles also include a second coating comprising an SCRcatalyst. In some embodiments, the platinum is fixed on the support insolution, i.e. in-situ. The catalysts and specific configurations aredescribed in further detail below.

Platinum on a Support/Ammonia Oxidation Catalysts

Embodiments of the present invention include platinum on a support,which may be included as an ammonia oxidation catalyst in catalystarticles as described herein. Preferably, the support includes a zeoliteand/or a SiO₂-Al₂O₃ mixed oxide. In some embodiments, the platinum maybe fixed on the support in solution, i.e. by in-situ Pt-fixing.

Catalytic articles of the present invention include platinum on asupport, where the support includes a zeolite and/or a SiO₂-Al₂O₃ mixedoxide. In some embodiments, the platinum is present on the support in anamount of about 0.5 wt % to about 10 wt % of the total weight of theplatinum and the support; about 1 wt % to about 6 wt % of the totalweight of the platinum and the support; about 1.5 wt % to about 4 wt %of the total weight of the platinum and the support; about 10 wt % ofthe total weight of the platinum and the support; about 0.5 wt % of thetotal weight of the platinum and the support; about 1 wt % of the totalweight of the platinum and the support; about 2 wt % of the total weightof the platinum and the support; about 3 wt % of the total weight of theplatinum and the support; about 4 wt % of the total weight of theplatinum and the support; about 5 wt % of the total weight of theplatinum and the support; about 6 wt % of the total weight of theplatinum and the support; about 7 wt % of the total weight of theplatinum and the support; about 8 wt % of the total weight of theplatinum and the support; about 9 wt % of the total weight of theplatinum and the support; or about 10 wt % of the total weight of theplatinum and the support.

In embodiments where platinum is supported on a SiO₂-Al₂O₃ mixed oxide,the SiO₂ may be present in an amount of about 1 wt % to about 80 wt % ofthe mixed oxide; about 1 wt % to about 75 wt % of the mixed oxide; about1 wt % to about 70 wt % of the mixed oxide; about 5 wt % to about 70 wt% of the mixed oxide; about 10 wt % to about 70 wt % of the mixed oxide;about 20 wt % to about 70 wt % of the mixed oxide; about 30 wt % toabout 70 wt % of the mixed oxide; about 40 wt % to about 70 wt % of themixed oxide; about 50 wt % to about 60 wt % of the mixed oxide; about 1wt % of the mixed oxide; about 5 wt % of the mixed oxide; about 10 wt %of the mixed oxide; about 20 wt % of the mixed oxide; about 30 wt % ofthe mixed oxide; about 40 wt % of the mixed oxide; about 50 wt % of themixed oxide; about 60 wt % of the mixed oxide; about 70 wt % of themixed oxide; about 75 wt % of the mixed oxide; or about 80 wt % of themixed oxide.

In embodiments where platinum is supported on a zeolite, a suitablezeolite may have an external surface area of at least about 30 m²/g; atleast about 40 m²/g; at least about 50 m²/g; at least about 60 m²/g; atleast about 70 m²/g; at least about 80 m²/g; at least about 90 m²/g; orat least about 100 m²/g. In some embodiments, a suitable zeolite mayhave an average crystal size of about 2 μm or less; about 1.5 μm orless; about 1 μm or less; about 0.5 μm or less; about 0.3 μm or less;less than about 2 μm; less than about 1.5 μm; less than about 1 μm; lessthan about 0.5 μm; less than about 0.3 μm; about 0.1 μm to about 2 μm;about 0.3 μm to about 1.5 μm; or about 0.5 μm to about 1 μm. Notably,particle size may be significantly different than a zeolite crystalsize, as a particle may consist of aggregates of many smaller crystals.In some embodiments, a suitable zeolite has a silica-to-alumina ratio ofat least 100; at least 200; at least 250; at least 300; at least 400; atleast 500; at least 600; at least 750; at least 800; or at least 1000.Zeolites are described in further detail in the SCR catalyst sectionbelow. In some embodiments, a suitable zeolite for supporting platinumis selected from the group of Framework Types consisting of ACO, AEI,AEN, AFN, AFT, AFX, ANA, APC, APD, ATT, CDO, CHA, DDR, DFT, EAB, EDI,EPI, ERI, GIS, GOO, IHW, ITE, ITW, LEV, KFI, MER, MON, NSI, OWE, PAU,PHI, RHO, RTH, SAT, SAV, SIV, THO, TSC, UEI, UFI, VNI, YUG, ZON, BEA,MFI and FER and mixtures and/or intergrowths thereof. In someembodiments, a suitable zeolite for selecting platinum is selected fromthe group of Framework Types consisting of CHA, LEV, AEI, AFX, ERI, SFW,KFI, DDR, ITE, BEA, MFI and FER

Catalyst articles of the present invention may include one or moreammonia oxidation catalysts, also called an ammonia slip catalyst(“ASC”). A preferred ammonia oxidation catalyst includes platinum on asupport, as described above, however, other or additional ammoniaoxidation catalyst may be included in embodiments of the presentinvention. One or more ammonia oxidation catalysts may be included withor downstream from an SCR catalyst, to oxidize excess ammonia andprevent it from being released to the atmosphere. In some embodimentsthe ammonia oxidation catalyst may be included on the same substrate asan SCR catalyst, or blended with an SCR catalyst. In certainembodiments, the ammonia oxidation catalyst material may be selected andformulated to favor the oxidation of ammonia instead of the formation ofNO_(x) or N₂O. Generally preferred catalyst materials include platinum,palladium, or a combination thereof. The ammonia oxidation catalyst maycomprise platinum and/or palladium supported on a metal oxide. In someembodiments, the catalyst is disposed on a high surface area support,including but not limited to alumina.

In some embodiments, an ammonia oxidation catalyst comprises a platinumgroup metal on a siliceous support. A siliceous material may include amaterial such as: (1) silica; (2) a zeolite with a silica-to-aluminaratio of at least 200; and (3) amorphous silica-doped alumina with SiO₂content >40%. In some embodiments, a siliceous material may include amaterial such as a zeolite with a silica-to-alumina ratio of at least200; at least 250; at least 300; at least 400; at least 500; at least600; at least 750; at least 800; or at least 1000. In some embodiments,a platinum group metal is present on the support in an amount of about0.5 wt % to about 10 wt % of the total weight of the platinum groupmetal and the support; about 1 wt % to about 6 wt % of the total weightof the platinum group metal and the support; about 1.5 wt % to about 4wt % of the total weight of the platinum group metal and the support;about 10 wt % of the total weight of the platinum group metal and thesupport; about 0.5 wt % of the total weight of the platinum group metaland the support; about 1 wt % of the total weight of the platinum groupmetal and the support; about 2 wt % of the total weight of the platinumgroup metal and the support; about 3 wt % of the total weight of theplatinum group metal and the support; about 4 wt % of the total weightof the platinum group metal and the support; about 5 wt % of the totalweight of the platinum group metal and the support; about 6 wt % of thetotal weight of the platinum group metal and the support; about 7 wt %of the total weight of the platinum group metal and the support; about 8wt % of the total weight of the platinum group metal and the support;about 9 wt % of the total weight of the platinum group metal and thesupport; or about 10 wt % of the total weight of the platinum groupmetal and the support.

In some embodiments, the siliceous support can comprise a molecularsieve having a BEA, CDO, CON, FAU, MEL, MFI or MWW Framework Type.

SCR Catalyst

Systems of the present invention may include one or more SCR catalyst.In some embodiments, a catalyst article may include a first SCR catalystand a second SCR catalyst. In some embodiments, the first SCR catalystand the second SCR catalyst may comprise the same formulation as eachother. In some embodiments, the first SCR catalyst and the second SCRcatalyst may comprise different formulations than each other. In someaspects, the first SCR catalyst comprises a Cu- and Mn-exchangedmolecular sieve, as described in further detail below.

In some aspects, a catalyst article may include an SCR catalyst blendedwith supported platinum. In some aspects, a catalyst article may includean SCR catalyst blended with supported platinum, where the SCR catalystcomprises a Cu- and Mn-exchanged molecular sieve. In some aspects, inaddition to the blend, a catalyst article may also include a secondcoating comprising an SCR catalyst.

The selective catalytic reduction composition may comprise, or consistessentially of, a metal oxide based SCR catalyst formulation, a basemetal based SCR catalyst formulation, a molecular sieve based SCRcatalyst formulation, a metal exchanged molecular sieve, or mixturesthereof. Such SCR catalyst formulations are known in the art. Typicalcompositions are generally described in U.S. Pat. Nos. 4,010,238 and4,085,193, the entire contents of which are incorporated herein byreference.

The selective catalytic reduction composition may comprise, or consistessentially of, a metal oxide based SCR catalyst formulation. The metaloxide based SCR catalyst formulation comprises vanadium or tungsten or amixture thereof supported on a refractory oxide. The refractory oxidemay be selected from the group consisting of alumina, silica, titania,zirconia, ceria and combinations thereof.

The metal oxide based SCR catalyst formulation may comprise, or consistessentially of, an oxide of vanadium (e.g. V₂O₅) and/or an oxide oftungsten (e.g. WO₃) supported on a refractory oxide selected from thegroup consisting of titania (e.g. TiO₂), ceria (e.g. CeO₂), and a mixedor composite oxide of cerium and zirconium (e.g. Ce_(x)Zr_((1-x))O₂,wherein x=0.1 to 0.9, preferably x=0.2 to 0.5).

When the refractory oxide is titania (e.g. TiO₂), then preferably theconcentration of the oxide of vanadium is from 0.5 to 6 wt % (e.g. ofthe metal oxide based SCR formulation) and/or the concentration of theoxide of tungsten (e.g. WO₃) is from 5 to 20 wt %. More preferably, theoxide of vanadium (e.g. V₂O₅) and the oxide of tungsten (e.g. WO₃) aresupported on titania (e.g. TiO₂). These catalysts may contain otherinorganic materials such as SiO₂ and ZrO₂ acting as binders andpromoters.

When the refractory oxide is ceria (e.g. CeO₂), then preferably theconcentration of the oxide of vanadium is from 0.1 to 9 wt % (e.g. ofthe metal oxide based SCR formulation) and/or the concentration of theoxide of tungsten (e.g. WO₃) is from 0.1 to 9 wt %.

The metal oxide based SCR catalyst formulation may comprise, or consistessentially of, an oxide of vanadium (e.g. V₂O₅) and optionally an oxideof tungsten (e.g. WO₃), supported on titania (e.g. TiO₂).

The selective catalytic reduction composition may comprise, or consistessentially of, a base metal based SCR catalyst formulation. Suitablebase metals may include vanadium (V), molybdenum (Mo) and tungsten (W),chromium (Cr), cerium (Ce), manganese (Mn), iron (Fe), cobalt (Co),nickel (Ni), and copper (Cu), and mixtures thereof.

When the SCR catalyst is a base metal or mixed base metal oxide, thecatalyst article can further comprise at least one base metal promoter.As used herein, a “promoter” is understood to mean a substance that whenadded into a catalyst, increases the activity of the catalyst. The basemetal promoter can be in the form of a metal, an oxide of the metal, ora mixture thereof. The at least one base metal catalyst promoter may beselected from neodymium (Nd), barium (Ba), cerium (Ce), lanthanum (La),praseodymium (Pr), magnesium (Mg), calcium (Ca), manganese (Mn), zinc(Zn), niobium (Nb), zirconium (Zr), molybdenum (Mo), tin (Sn), tantalum(Ta), strontium (Sr) and oxides thereof. The at least one base metalcatalyst promoter can preferably be MnO₂, Mn₂O₃, Fe₂O₃, SnO₂, CuO, CoO,CeO₂ and mixtures thereof. The at least one base metal catalyst promotermay be added to the catalyst in the form of a salt in an aqueoussolution, such as a nitrate or an acetate. The at least one base metalcatalyst promoter and at least one base metal catalyst, e.g., copper,may be impregnated from an aqueous solution onto the oxide supportmaterial(s), may be added into a washcoat comprising the oxide supportmaterial(s), or may be impregnated into a support previously coated withthe washcoat.

The selective catalytic reduction composition may comprise, or consistessentially of, a molecular sieve based SCR catalyst formulation. Themolecular sieve based SCR catalyst formulation comprises a molecularsieve, which is optionally a transition metal exchanged molecular sieve.It is preferable that at least one of the SCR catalyst formulationscomprises a transition metal exchanged molecular sieve.

In general, the molecular sieve based SCR catalyst formulation maycomprise a molecular sieve having an aluminosilicate framework (e.g.zeolite), an aluminophosphate framework (e.g. AlPO), asilicoaluminophosphate framework (e.g. SAPO), a heteroatom-containingaluminosilicate framework, a heteroatom-containing aluminophosphateframework (e.g. MeAlPO, where Me is a metal), or a heteroatom-containingsilicoaluminophosphate framework (e.g. MeAPSO, where Me is a metal), ormixtures thereof. The heteroatom (i.e. in a heteroatom-containingframework) may be selected from the group consisting of boron (B),gallium (Ga), titanium (Ti), zirconium (Zr), zinc (Zn), iron (Fe),vanadium (V) and combinations of any two or more thereof. It ispreferred that the heteroatom is a metal (e.g. each of the aboveheteroatom-containing frameworks may be a metal-containing framework).

It is preferable that the molecular sieve based SCR catalyst formulationcomprises, or consist essentially of, a molecular sieve having analuminosilicate framework (e.g. zeolite) or a silicoaluminophosphateframework (e.g. SAPO). A zeolitic molecular sieve is a microporousaluminosilicate having any one of the framework structures listed in theDatabase of Zeolite Structures published by the International ZeoliteAssociation (IZA). The framework structures include, but are not limitedto those of the CHA, FAU, BEA, MFI, MOR types. Non-limiting examples ofzeolites having these structures include chabazite, faujasite, zeoliteY, ultrastable zeolite Y, beta zeolite, mordenite, silicalite, zeoliteX, and ZSM-5.

When the molecular sieve has an aluminosilicate framework (e.g. themolecular sieve is a zeolite), then typically the molecular sieve has asilica to alumina molar ratio (SAR) of from 5 to 200 (e.g. 10 to 200),10 to 100 (e.g. 10 to 30 or 20 to 80), such as 12 to 40, or 15 to 30. Insome embodiments, a suitable molecular sieve has a SAR of >200; >600;or >1200. In some embodiments, the molecular sieve has a SAR of fromabout 1500 to about 2100.

Typically, the molecular sieve is microporous. A microporous molecularsieve has pores with a diameter of less than 2 nm (e.g. in accordancewith the IUPAC definition of “microporous” [see Pure & Appl. Chem.,66(8), (1994), 1739-1758)]).

The molecular sieve based SCR catalyst formulation may comprise a smallpore molecular sieve (e.g. a molecular sieve having a maximum ring sizeof eight tetrahedral atoms), a medium pore molecular sieve (e.g. amolecular sieve having a maximum ring size of ten tetrahedral atoms) ora large pore molecular sieve (e.g. a molecular sieve having a maximumring size of twelve tetrahedral atoms) or a combination of two or morethereof.

When the molecular sieve is a small pore molecular sieve, then the smallpore molecular sieve may have a framework structure represented by aFramework Type Code (FTC) selected from the group consisting of ACO,AEI, AEN, AFN, AFT, AFX, ANA, APC, APD, ATT, CDO, CHA, DDR, DFT, EAB,EDI, EPI, ERI, GIS, GOO, IHW, ITE, ITW, LEV, LTA, KFI, MER, MON, NSI,OWE, PAU, PHI, RHO, RTH, SAT, SAV, SFW, SIV, THO, TSC, UEI, UFI, VNI,YUG and ZON, or a mixture and/or an intergrowth of two or more thereof.Preferably, the small pore molecular sieve has a framework structurerepresented by a FTC selected from the group consisting of CHA, LEV,AEI, AFX, EM, ERI, LTA, SFW, KFI, DDR and ITE. More preferably, thesmall pore molecular sieve has a framework structure represented by aFTC selected from the group consisting of CHA and AEI. The small poremolecular sieve may have a framework structure represented by the FTCCHA. The small pore molecular sieve may have a framework structurerepresented by the FTC AEI. When the small pore molecular sieve is azeolite and has a framework represented by the FTC CHA, then the zeolitemay be chabazite.

When the molecular sieve is a medium pore molecular sieve, then themedium pore molecular sieve may have a framework structure representedby a Framework Type Code (FTC) selected from the group consisting ofAEL, AFO, AHT, BOF, BOZ, CGF, CGS, CHI, DAC, EUO, FER, HEU, IMF, ITH,ITR, JRY, JSR, JST, LAU, LOV, MEL, MFI, MFS, MRE, MTT, MVY, MWW, NAB,NAT, NES, OBW, -PAR, PCR, PON, PUN, RRO, RSN, SFF, SFG, STF, STI, STT,STW, -SVR, SZR, TER, TON, TUN, UOS, VSV, WEI and WEN, or a mixtureand/or an intergrowth of two or more thereof. Preferably, the mediumpore molecular sieve has a framework structure represented by a FTCselected from the group consisting of FER, MEL, MFI, and STT. Morepreferably, the medium pore molecular sieve has a framework structurerepresented by a FTC selected from the group consisting of FER and MFI,particularly MFI. When the medium pore molecular sieve is a zeolite andhas a framework represented by the FTC FER or MFI, then the zeolite maybe ferrierite, silicalite, or ZSM-5.

When the molecular sieve is a large pore molecular sieve, then the largepore molecular sieve may have a framework structure represented by aFramework Type Code (FTC) selected from the group consisting of AFI,AFR, AFS, AFY, ASV, ATO, ATS, BEA, BEC, BOG, BPH, BSV, CAN, CON, CZP,DFO, EMT, EON, EZT, FAU, GME, GON, IFR, ISV, ITG, IWR, IWS, IWV, IWW,JSR, LTF, LTL, MAZ, MEI, MOR, MOZ, MSE, MTW, NPO, OFF, OKO, OSI, -RON,RWY, SAF, SAO, SBE, SBS, SBT, SEW, SFE, SFO, SFS, SFV, SOF, SOS, STO,SSF, SSY, USI, UWY, and VET, or a mixture and/or an intergrowth of twoor more thereof. Preferably, the large pore molecular sieve has aframework structure represented by a FTC selected from the groupconsisting of AFI, BEA, MAZ, MOR, and OFF. More preferably, the largepore molecular sieve has a framework structure represented by a FTCselected from the group consisting of BEA, MOR and MFI. When the largepore molecular sieve is a zeolite and has a framework represented by theFTC BEA, FAU or MOR, then the zeolite may be a beta zeolite, faujasite,zeolite Y, zeolite X or mordenite.

The molecular sieve based SCR catalyst formulation preferably comprisesa transition metal exchanged molecular sieve. A metal exchangedmolecular sieve can have at least one metal from one of the groups VB,VIB, VIIB, VIIIB, IB, or IIB of the periodic table deposited ontoextra-framework sites on the external surface or within the channels,cavities, or cages of the molecular sieves. Metals may be in one ofseveral forms, including, but not limited to, zero valent metal atoms orclusters, isolated cations, mononuclear or polynuclear oxycations, or asextended metal oxides. The transition metal may be selected from thegroup consisting of cobalt, copper, iron, manganese, nickel, palladium,platinum, ruthenium, rhenium, and combinations thereof.

The transition metal may be present on an extra-framework site on theexternal surface of the molecular sieve or within a channel, cavity orcage of the molecular sieve.

Typically, the transition metal exchanged molecular sieve comprisestransition metal in an amount of 0.10 to 10% by weight of the transitionmetal exchanged molecular sieve, preferably an amount of 0.2 to 5% byweight.

In some aspects, the metal exchanged molecular sieve can be aCu-exchanged small pore molecular sieve having from about 0.1 to about20.0 wt. % copper of the total weight of the catalyst. In some aspects,copper is present from about 0.5 wt. % to about 15 wt. % of the totalweight of the catalyst. In some aspects, copper is present from about 1wt. % to about 9 wt. % of the total weight of the catalyst.

Cu- and Mn-Exchanged Molecular Sieve

A blend of the present invention may include an SCR catalyst comprisinga Cu- and Mn-exchanged molecular sieve. Additionally, in some aspects, asecond SCR catalyst may include a Cu- and Mn-exchanged molecular sieve.

In some aspects, the metal exchanged molecular sieve includes amolecular sieve with exchanged copper and exchanged manganese. In someaspects, the molecular sieve is free of, or essentially free of anyadditional transition metals. For example, in some aspects, themolecular sieve contains additional transition metals (i.e., further tothe exchanged copper and exchanged manganese) in an amount less thanabout 1 wt %; less than about 0.7 wt %; less than about 0.5 wt %; lessthan about 0.3 wt %; less than about 0.1 wt %; less than about 0.07 wt%; less than about 0.05 wt %; or less than about 0.01 wt %, based on theweight of the molecular sieve. In some aspects, the molecular sieve maybe described as bimetallic, as the molecular sieve includes twotransition metals.

In some aspects, a transition metal exchanged molecular sieve comprisesexchanged copper and exchanged manganese in a combined amount of about0.10 to about 10% by weight of the transition metal exchanged molecularsieve; about 0.1 to about 7% by weight of the transition metal exchangedmolecular sieve; about 0.2 to about 7% by weight of the transition metalexchanged molecular sieve; about 0.2 to about 5% by weight of thetransition metal exchanged molecular sieve; about 0.5 to about 6% byweight of the transition metal exchanged molecular sieve; about 1 toabout 7% by weight of the transition metal exchanged molecular sieve;about 1 to about 5% by weight of the transition metal exchangedmolecular sieve; about 2 to about 5% by weight of the transition metalexchanged molecular sieve; about 1.5 to about 3% by weight of thetransition metal exchanged molecular sieve; about 1.5 to 4% by weight ofthe transition metal exchanged molecular sieve; or about 2 to about 4%by weight of the transition metal exchanged molecular sieve.

In some aspects, a transition metal exchanged molecular sieve of thepresent invention comprises exchanged copper in an amount of about 0.05to about 7% by weight of the transition metal exchanged molecular sieve;about 0.5 to about 5% by weight of the transition metal exchangedmolecular sieve; about 0.05 to about 5% by weight of the transitionmetal exchanged molecular sieve; about 0.1 to about 4% by weight of thetransition metal exchanged molecular sieve; about 0.1 to about 3% byweight of the transition metal exchanged molecular sieve; about 0.2 toabout 3% by weight of the transition metal exchanged molecular sieve;about 0.5 to about 2.5% by weight of the transition metal exchangedmolecular sieve; about 1 to about 4% by weight of the transition metalexchanged molecular sieve; or about 1 to about 2% by weight of thetransition metal exchanged molecular sieve.

In some aspects, a transition metal exchanged molecular sieve of thepresent invention comprises exchanged manganese in an amount of about0.05 to about 7% by weight of the transition metal exchanged molecularsieve, about 0.05 to about 5% by weight of the transition metalexchanged molecular sieve; about 0.1 to about 5% by weight of thetransition metal exchanged molecular sieve; about 0.1 to about 4% byweight of the transition metal exchanged molecular sieve; about 0.1 toabout 3% by weight of the transition metal exchanged molecular sieve;about 0.2 to about 3% by weight of the transition metal exchangedmolecular sieve; about 0.5 to about 2.5% by weight of the transitionmetal exchanged molecular sieve; or about 1 to about 2% by weight of thetransition metal exchanged molecular sieve.

In some aspects, a transition metal exchanged molecular sieve of thepresent invention comprises exchanged copper and exchanged manganese ina weight ratio of about 1:1. In some aspects, a transition metalexchanged molecular sieve of the present invention comprises exchangedcopper and exchanged manganese in a weight ratio of about 0.1 to about50; about 0.2 to about 15; or about 0.33 to about 3. In some aspects, inaddition to utilizing the above-mentioned copper and manganese ratios,the exchange capacity of the molecular sieve in terms of metal ion toexchange site ratio should be <1; <0.75; or <0.5. In some aspects, atransition exchanged molecular sieve has a transition metal to aluminumratio of <1; <0.75; or <0.5.

Catalysts of the present invention can be prepared by any suitable meansknown in the art, including, for example, one pot, prefixing, and spraydrying.

In general, the selective catalytic reduction catalyst comprises theselective catalytic reduction composition in a total concentration of0.5 to 4.0 g in preferably 1.0 to 3.0 4.0 g in⁻³.

The SCR catalyst composition may comprise a mixture of a metal oxidebased SCR catalyst formulation and a molecular sieve based SCR catalystformulation. The (a) metal oxide based SCR catalyst formulation maycomprise, or consist essentially of, an oxide of vanadium (e.g. V₂O₅)and optionally an oxide of tungsten (e.g. WO₃), supported on titania(e.g. TiO₂) and (b) the molecular sieve based SCR catalyst formulationmay comprise a transition metal exchanged molecular sieve.

An exhaust system of embodiments of the present invention may include anSCR catalyst which is positioned downstream of an injector forintroducing ammonia or a compound decomposable to ammonia into theexhaust gas. The SCR catalyst may be positioned directly downstream ofthe injector for injecting ammonia or a compound decomposable to ammonia(e.g. there is no intervening catalyst between the injector and the SCRcatalyst).

Blend

Embodiments of the present invention may include a blend of (1) platinumon a support, and (2) an SCR catalyst comprising a Cu- and Mn-exchangedmolecular sieve. In some embodiments, within the blend, a weight ratioof the SCR catalyst to the platinum on a support is about 3:1 to about300:1; about 3:1 to about 250:1; about 3:1 to about 200:1; about 4:1 toabout 150:1; about 5:1 to about 100:1; about 6:1 to about 90:1; about7:1 to about 80:1; about 7:1 to about 100:1; about 8:1 to about 70:1;about 9:1 to about 60:1; about 10:1 to about 50:1; about 3:1; about 4:1;about 5:1; about 6:1; about 7:1; about 8:1; about 9:1; about 10:1; about15:1; about 20:1; about 25:1; about 30:1; about 40:1; about 50:1; about75:1; about 100:1; about 125:1; about 150:1; about 175:1; about 200:1;about 225:1; about 250:1; about 275:1; or about 300:1.

The term “active component loading” refers to the weight of the supportof platinum+the weight of platinum+the weight of the first SCR catalystin the blend. In some embodiments, platinum is present in an activecomponent loading from about 0.01 wt % to about 0.25 wt %, inclusive;about 0.04 wt % to about 0.2 wt %, inclusive; about 0.07 wt % to about0.17 wt %, inclusive; about 0.05 wt % to about 0.15 wt %, inclusive;about 0.01 wt %; about 0.02 wt %; about 0.03 wt %; about 0.04 wt %;about 0.05 wt %; about 0.06 wt %; about 0.07 wt %; about 0.08 wt %;about 0.1 wt %; about 0.12 wt %; about 0.15 wt %; about 0.17 wt %; about0.2 wt %; about 0.22 wt %; or about 0.25 wt %.

In some embodiments, the blend comprising platinum on the support and anSCR catalyst further comprises at least one of palladium (Pd), gold (Au)silver (Ag), ruthenium (Ru) or rhodium (Rh).

Substrate

Catalysts of the present invention may each further comprise aflow-through substrate or filter substrate. In one embodiment, thecatalyst may be coated onto the flow-through or filter substrate, andpreferably deposited on the flow-through or filter substrate using awashcoat procedure.

The combination of an SCR catalyst and a filter is known as a selectivecatalytic reduction filter (SCRF catalyst). An SCRF catalyst is asingle-substrate device that combines the functionality of an SCR andparticulate filter, and is suitable for embodiments of the presentinvention as desired. Description of and references to the SCR catalystthroughout this application are understood to include the SCRF catalystas well, where applicable. In general for an SCRF, the selectivecatalytic reduction composition is disposed within the wall of thewall-flow filter substrate monolith. Additionally, the selectivecatalytic reduction composition may be disposed on the walls of theinlet channels and/or on the walls of the outlet channels.

The flow-through or filter substrate is a substrate that is capable ofcontaining catalyst/adsorber components. The substrate is preferably aceramic substrate or a metallic substrate. The ceramic substrate may bemade of any suitable refractory material, e.g., alumina, silica,titania, ceria, zirconia, magnesia, zeolites, silicon nitride, siliconcarbide, zirconium silicates, magnesium silicates, aluminosilicates,metallo aluminosilicates (such as cordierite and spudomene), or amixture or mixed oxide of any two or more thereof. Cordierite, amagnesium aluminosilicate, and silicon carbide are particularlypreferred.

The metallic substrates may be made of any suitable metal, and inparticular heat-resistant metals and metal alloys such as titanium andstainless steel as well as ferritic alloys containing iron, nickel,chromium, and/or aluminum in addition to other trace metals.

The flow-through substrate is preferably a flow-through monolith havinga honeycomb structure with many small, parallel thin-walled channelsrunning axially through the substrate and extending throughout from aninlet or an outlet of the substrate. The channel cross-section of thesubstrate may be any shape, but is preferably square, sinusoidal,triangular, rectangular, hexagonal, trapezoidal, circular, or oval. Theflow-through substrate may also be high porosity which allows thecatalyst to penetrate into the substrate walls.

The filter substrate is preferably a wall-flow monolith filter. Thechannels of a wall-flow filter are alternately blocked, which allow theexhaust gas stream to enter a channel from the inlet, then flow throughthe channel walls, and exit the filter from a different channel leadingto the outlet. Particulates in the exhaust gas stream are thus trappedin the filter.

The catalyst/adsorber may be added to the flow-through or filtersubstrate by any known means, such as a washcoat procedure.

Configurations

Embodiments of the present invention relate to catalytic articles havinga first coating and a second coating, wherein the first coating includesa blend of (1) platinum of a support, and (2) a first SCR catalystcomprising a Cu- and Mn-exchanged molecular sieve, and the secondcoating including a second SCR catalyst. The catalytic articles may beprepared with various configurations. In some embodiments, the coatingsare arranged such that the exhaust gas contacts the second coatingbefore contacting the first coating. In some embodiments, the second SCRcatalyst is located on the inlet side of the blend. In some embodiments,the SCR catalyst is located on the outlet side of the blend.

In a first configuration, a catalyst can comprise a first coatingcomprising a blend of (1) platinum on a support and (2) a first SCRcatalyst comprising a Cu- and Mn-exchanged molecular sieve, and a secondcoating comprising a second SCR catalyst, where the second coating islocated in a layer over the first coating and the second coating coversall of the first coating. FIG. 1 depicts an example of thisconfiguration, in which the second SCR is positioned in the exhaust gasflow over the blend and the second SCR covers the entire blend.

In a second configuration, a catalyst can comprise a first coatingcomprising a blend of (1) platinum on a support and (2) a first SCRcatalyst comprising a Cu- and Mn-exchanged molecular sieve, and a secondcoating comprising a second SCR catalyst, where the first coatingextends from the outlet end toward the inlet end, covering less than afull length of the substrate, and the second coating extends the entirelength of the substrate, completely overlapping the first coating. FIG.2 depicts an example of this configuration, in which the second SCR ispositioned in the exhaust gas flow before the blend and the second SCRcompletely overlaps the blend.

In a third configuration, a catalyst can comprise a first coatingcomprising a blend of (1) platinum on a support and (2) a first SCRcatalyst comprising a Cu- and Mn-exchanged molecular sieve, and a secondcoating comprising a second SCR catalyst, where the first coatingextends from the outlet end toward the inlet end, covering less than afull length of the substrate, and the second coating extends from theinlet end towards the outlet end, partially overlapping the firstcoating. The second SCR catalyst can overlap the first coating by anamount from about 10% to about 95%, inclusive, preferably about 50% toabout 95%, inclusive. FIG. 3 depicts an example of this configuration,in which the second SCR is positioned in the exhaust gas flow before theblend and the second SCR covers a portion, but not all, of the blend. InFIG. 3, the second SCR covers about 40% of the blend.

In a fourth configuration, a catalyst can comprise a first coatingcomprising a blend of (1) platinum on a support and (2) a first SCRcatalyst comprising a Cu- and Mn-exchanged molecular sieve, and a secondcoating comprising a second SCR catalyst, where the first coatingextends from the outlet end toward the inlet end, covering less than afull length of the substrate, and the second coating extends from theinlet end towards the outlet end, without overlapping the first coating.There may be a space between the first coating and the second coating,the first coating and the second coating may meet but not overlap, orthere may be a slight and insubstantial overlap of the first and secondcoating. FIG. 4 depicts an example of this configuration, in which thesecond SCR is positioned in the exhaust gas flow before the blend andthe second SCR meets but does not overlap the blend.

In a fifth configuration, a catalyst can comprise a first coatingcomprising a blend of (1) platinum on a support and (2) a first SCRcatalyst comprising a Cu- and Mn-exchanged molecular sieve, and a secondcoating comprising a second SCR catalyst, where the first coatingextends from the inlet end toward the outlet end, covering less than afull length of the substrate, and the second coating extends the entirelength of the substrate, completely overlapping the first coating. FIG.5 depicts an example of this configuration, in which the second SCRcovers the entire blend and a portion of the second SCR is positioned inthe exhaust gas flow after the blend.

In a sixth configuration, a catalyst can comprise a first coatingcomprising a blend of (1) platinum on a support and (2) a first SCRcatalyst comprising a Cu- and Mn-exchanged molecular sieve, and a secondcoating comprising a second SCR catalyst, where the first coatingextends from the inlet end toward the outlet end, covering less than afull length of the substrate, and the second coating extends from theoutlet end toward the inlet end, covering less than the full length ofthe substrate, and partially overlapping the first coating. The secondSCR catalyst can overlap the blend by an amount from about 10% to about95%, inclusive, preferably about 50% to about 95% inclusive. FIG. 6depicts an example of this configuration, in which the second SCR coversa portion of, but not the entire blend, and a portion of the second SCRis positioned in the exhaust gas flow after the blend. In FIG. 6, thesecond SCR covers about 95% of the blend.

In a seventh configuration, a catalyst can comprise a first layercomprising a third SCR catalyst. The first layer may be partially, butnot completely, covered by a coating comprising a blend of (1) platinumon a support and (2) a first SCR catalyst comprising a Cu- andMn-exchanged molecular sieve. The blend can cover the third SCR catalystin an amount from about 10% to about 95%, inclusive, preferably about50% to about 95%, inclusive. The blend may be covered by a coatingcomprising a second SCR catalyst, where the second SCR catalyst coatingcovers the entire blend coating. FIG. 7 depicts an example of thisconfiguration, in which a third SCR catalyst is a bottom layer on asubstrate, with a second layer comprising the blend, partially coveringthe third SCR catalyst, and a third layer, comprising a second SCR,positioned over the second layer and covering all of the blend layer.

In an eighth configuration, a catalyst can comprise a first layercomprising a third SCR catalyst. The first layer may be partially, butnot completely, covered by a coating comprising a blend of (1) platinumon a support and (2) a first SCR catalyst comprising a Cu- andMn-exchanged molecular sieve. The blend can cover the third SCR catalystin an amount from about 10% to about 95%, inclusive, preferably about50% to about 95%. The blend may be covered by a coating comprising asecond SCR catalyst, where the second SCR catalyst coating partially,but not completely, covers the blend coating, and a portion of thesecond SCR catalyst coating is also located downstream of the blend andalso covers a portion of the third SCR catalyst downstream from theblend coating. The second SCR catalyst can cover the third SCR catalystin an amount from about 10% to about 95%, inclusive, preferably about50% to about 95%, inclusive. FIG. 8 depicts an example of thisconfiguration, in which a third SCR catalyst is a bottom layer on asubstrate, with a second layer comprising the blend, partially, but notcompletely, covering the third SCR catalyst, and a third layer,comprising a second SCR catalyst, positioned over the second layer andpartially, but not completely, covering the blend layer. In FIG. 8, theblend layer covers about 60% of the first layer and the layer with thesecond SCR catalyst covers about 20% of the first layer. The term“cover” means the portion of a layer that is in direct contact with adifferent layer.

Reductant/Urea Injector

Systems of some embodiments of the present invention may include a meansfor introducing a nitrogenous reductant into the exhaust system upstreamof the ammonia slip catalyst. It may be preferred that the means forintroducing a nitrogenous reductant into the exhaust system is directlyupstream of the ammonia slip catalyst (e.g. there is no interveningcatalyst between the means for introducing a nitrogenous reductant andthe ammonia slip catalyst).

The reductant is added to the flowing exhaust gas by any suitable meansfor introducing the reductant into the exhaust gas. Suitable meansinclude an injector, sprayer, or feeder. Such means are well known inthe art.

The nitrogenous reductant for use in the system can be ammonia per se,hydrazine, or an ammonia precursor selected from the group consisting ofurea, ammonium carbonate, ammonium carbamate, ammonium hydrogencarbonate, and ammonium formate. Urea is particularly preferred.

The exhaust system may also comprise a means for controlling theintroduction of reductant into the exhaust gas in order to reduce NOxtherein. Preferred control means may include an electronic control unit,optionally an engine control unit, and may additionally comprise a NOxsensor located downstream of the NO reduction catalyst.

Method of Making

Catalytic articles of some embodiments of the present invention may beprepared by any suitable means known in the art. For catalytic articlesincluding platinum on a support, such platinum may be fixed on thesupport in solution, i.e. in-situ, such that no separate pre-fixingprocess is required. To prepare a coating which includes a blend of (1)platinum on a support and (2) an SCR catalyst comprising a Cu- andMn-exchanged molecular sieve, the following steps may be performed:

-   -   Combine support material with water into a batch and mix;    -   Add an organic acid that acts as a reductant for platinum and/or        creates a reducing environment during the later calcinating        step. Examples of a suitable organic acid may include citric        acid, succinic acid, oxalic acid, ascorbic acid, acetic acid,        formic acid, and combinations thereof;    -   Add platinum nitrate into the batch, in an amount such that the        molar ratio of organic acid to platinum is 20:1 to 1:1; 10:1 to        1:1; or 5:1 to 1:1;    -   Combine the platinum batch with an SCR batch;    -   Adjust rheology and solids % of the combined batch, coat and        fire at 500° C. -550° C. in air.

Method of Using

A method of reducing emissions from an exhaust stream may includecontacting the exhaust stream with a catalytic article as describedherein. In some embodiments, a method of improving NH₃ conversion anexhaust gas at a temperature of about 300° C. or less may includecontacting an exhaust gas comprising ammonia with a catalytic article asdescribed herein. In some embodiments, a method of treating exhaust gascomprising ammonia and NOx may include contacting an exhaust gascomprising ammonia with a catalytic article as described herein. In someembodiments, the weight ratio of ammonia to NOx (ANR) in the exhaust gasis >1.0 for at least a portion of the operating time of the system

Benefits

Catalytic articles of the present invention may provide improvements incatalytic activity and selectivity. Ammonia slip catalysts which includea layer with a blend of (1) a platinum group metal on a support and (2)an SCR catalyst have provided improvements in both N₂O formation and NOxre-make, however, certain of these catalysts may exhibit drawbacksand/or limitations. Specifically, where such catalysts requirepre-fixing the platinum group metal on a support, such catalysts involvethe extra cost associated with the pre-fixing step, and may exhibitlower NH₃ conversion at low temperatures (such as below 300° C.), andunder challenging conditions (such as high NH₃ slip and/or high spacevelocity).

It has surprisingly been found that catalytic articles of the presentinvention may minimize or lessen such aforementioned drawbacks andlimitations. For example, by fixing a platinum group metal to a supportin solution, i.e. in-situ, the additional cost associated with thepre-fixing step is eliminated. Additionally, such catalytic articlesexhibit improved NH₃ conversion at low temperatures (such as below 300°C.), and under challenging conditions (such as high NH₃ slip and/or highspace velocity).

In some embodiments, catalytic articles of the present invention havinga platinum group metal which was fixed on a support in solution mayprovide equivalent or enhanced activity for NH₃ conversion attemperatures of about 300° C. or less compared to a catalytic articlewhich is equivalent except has a platinum group metal pre-fixed on asupport. In some embodiments, catalytic articles of the presentinvention having a platinum group metal which was fixed on a support insolution may have enhanced activity for NH₃ conversion at temperaturesof about 300° C. or less comparted to a catalytic article which isequivalent except has a platinum group metal pre-fixed on a support, theinventive catalytic article showing an improvement in NH₃ conversion attemperatures of about 300 C or less of about 30% to about 100%; about35% to about 95%; about 40% to about 90%; about 45% to about 85%; about50% to about 80%; about 55% to about 75%; about 30% to about 50%; about35% to about 55%; about 40% to about 60%; about 50% to about 70%; about60% to about 80%; about 70% to about 90%; about 80% to about 100%;greater than 30%; greater than 40%; greater than 50%; greater than 60%;greater than 70%; greater than 80%; or greater than 90%.

In some embodiments, catalytic articles of the present invention havingplatinum on a support comprising a high external surface area zeolite(>50 m²/g) or a SiO₂-Al₂O₃ mixed oxide may provide equivalent orenhanced activity for NH₃ conversion at temperatures of about 300° C. orless compared to a catalytic article which is equivalent except has aplatinum group metal fixed on a support other than a high externalsurface area zeolite (>50 m²/g) or a SiO₂-Al₂O₃ mixed oxide. In someembodiments, catalytic articles of the present invention having platinumon a support comprising a high external surface area zeolite (>50 m²/g)or a SiO₂-Al₂O₃ mixed oxide may provide equivalent or enhanced activityfor NH₃ conversion at temperatures of about 300° C. or less compared toa catalytic article which is equivalent except has a platinum groupmetal fixed on a support other than a high external surface area zeolite(>50 m²/g) or a SiO₂-Al₂O₃ mixed oxide, the inventive catalytic articleshowing an improvement in NH₃ conversion at temperatures of about 300 Cor less of about 30% to about 100%; about 35% to about 95%; about 40% toabout 90%; about 45% to about 85%; about 50% to about 80%; about 55% toabout 75%; about 30% to about 50%; about 35% to about 55%; about 40% toabout 60%; about 50% to about 70%; about 60% to about 80%; about 70% toabout 90%; about 80% to about 100%; greater than 30%; greater than 40%;greater than 50%; greater than 60%; greater than 70%; greater than 80%;or greater than 90%.

Further, additional benefits of have surprisingly been discovered whenusing Cu- and Mn-exchanged molecular sieve as part of blend.Specifically, using a Cu- and Mn-exchanged molecular sieve in the blendprovides an advantage of improved NH₃ conversion while maintaining thebenefits associated with the Cu-zeolite for N₂O formation and NOxre-make. In addition, it shows promises in tuning the catalyst activityversus selectivity by adjusting the Mn and Cu loadings and/or ratios.

Terms

As used in this specification and the appended claims, the singularforms “a”, “an” and “the” include plural referents unless the contextclearly indicates otherwise. Thus, for example, reference to “acatalyst” includes a mixture of two or more catalysts, and the like.

The term “ammonia slip”, means the amount of unreacted ammonia thatpasses through the SCR catalyst.

The term “support” means the material to which a catalyst is fixed.

The term “calcine”, or “calcination”, means heating the material in airor oxygen. This definition is consistent with the IUPAC definition ofcalcination. (IUPAC. Compendium of Chemical Terminology, 2nd ed. (the“Gold Book”). Compiled by A. D. McNaught and A. Wilkinson. BlackwellScientific Publications, Oxford (1997). XML on-line corrected version:http://goldbook.iupac.org (2006-) created by M. Nic, J. Jirat, B.Kosata; updates compiled by A. Jenkins. ISBN 0-9678550-9-8.doi:10.1351/goldbook.) Calcination is performed to decompose a metalsalt and promote the exchange of metal ions within the catalyst and alsoto adhere the catalyst to a substrate. The temperatures used incalcination depend upon the components in the material to be calcinedand generally are between about 400° C. to about 900° C. forapproximately 1 to 8 hours. In some cases, calcination can be performedup to a temperature of about 1200° C. In applications involving theprocesses described herein, calcinations are generally performed attemperatures from about 400° C. to about 700° C. for approximately 1 to8 hours, preferably at temperatures from about 400° C. to about 650° C.for approximately 1 to 4 hours.

When a range, or ranges, for various numerical elements are provided,the range, or ranges, can include the values, unless otherwisespecified.

The term “N₂ selectivity” means the percent conversion of ammonia intonitrogen.

The terms “diesel oxidation catalyst” (DOC), “diesel exotherm catalyst”(DEC), “NOx absorber”, “SCR/PNA” (selective catalytic reduction/passiveNOx adsorber), “cold-start catalyst” (CSC) and “three-way catalyst”(TWC) are well known terms in the art used to describe various types ofcatalysts used to treat exhaust gases from combustion processes.

The term “platinum group metal” or “PGM” refers to platinum, palladium,ruthenium, rhodium, osmium and iridium. The platinum group metals arepreferably platinum, palladium, ruthenium or rhodium.

The terms “downstream” and “upstream” describe the orientation of acatalyst or substrate where the flow of exhaust gas is from the inletend to the outlet end of the substrate or article.

The following examples merely illustrate the invention; the skilledperson will recognize many variations that are within the spirit of theinvention and scope of the claims.

EXAMPLES Example 1

In-situ blend catalysts were prepared including platinum on a supportblended with an SCR catalyst. Various catalysts were prepared, usingdifferent supports, as noted in Table 1 below.

To prepare the in-situ blend catalysts, in-situ platinum fixing wasused, i.e. platinum precursor was fixed onto the support in solution andtherefore no separate pre-fixing process is required, as describedbelow:

-   -   Combine support material with water into a batch and mix;    -   Add an organic acid that acts as a reductant for platinum and/or        creates a reducing environment during the later calcinating        step. Examples of a suitable organic acid may include citric        acid, succinic acid, oxalic acid, ascorbic acid, acetic acid,        formic acid, and combinations thereof;    -   Add platinum nitrate into the batch, in an amount such that the        molar ratio of organic acid to platinum is 20:1 to 1:1; 10:1 to        1:1; or 5:1 to 1:1;    -   Combine the platinum batch with an SCR batch;    -   Adjust rheology and solids % of the combined batch, coat and        fire at 500° C. -550° C. in air.

TABLE 1 Properties of the support materials used in in-situ fixing of PtAccessible surface area for Name Composition platinum (m²/g)* AluminaAl₂O₃ 140 Nano-alumina Al₂O₃ 220 Fumed silica SiO₂ 200 Silica gel SiO₂500 Silica-titania 10% SiO₂, 90% TiO₂ 110 Silica-alumina 40% SiO₂, 60%Al₂O₃ 500 zeolite MFI, SiO₂-to- Al₂O₃ ratio = 2000 5 Nano zeolite MFI,SiO₂-to- Al₂O₃ ratio = 400 80 *Note: total BET surface area are used foroxides; t-Plot external surface area are used for zeolites

The following catalysts were prepared:

Reference ASC:

A bi-layer formulation having a Pt on alumina bottom layer and an SCRtop layer was used as a reference exampl.

A bottom layer was applied to a ceramic substrate using a washcoatcomprising 0.17 wt % Pt on a blend of alumina and bare zeolite. Thewashcoat was applied to a ceramic substrate, then the washcoat waspulled down the substrate using a vacuum. The article was dried andcalcined at about 500° C. for about 1 hour. The loading of Pt on thearticle was 3 g/ft³.

A top layer was applied to the substrate coated with the bottom layerusing a second washcoat comprising a Cu-CHA, then the washcoat waspulled down the substrate using a vacuum. The article was dried andcalcined at about 500° C. for about 1 hour. The loading of CuCHA in thetop layer was 1.8 g/in³.

Pre-Fixed Pt-Zeolite Blend ASC:

A bottom layer was applied to a ceramic substrate using a washcoatcomprising a blend of 4 wt % Pt on a ZSM-5 (MFI framework with SAR=2000)and a Cu-CHA. The washcoat was applied to a ceramic substrate, then thewashcoat was pulled down the substrate using a vacuum. The article wasdried and calcined at about 500° C. for about 1 hour. The loading of Pt,the zeolite and the CuCHA on the article was 3 g/ft³, 0.045 g/in³, and0.9 g/in³, respectively.

A top layer was applied to the substrate coated with the bottom layerusing a second washcoat comprising a Cu-CHA, then the washcoat waspulled down the substrate to a distance of about 50% of the length ofthe substrate using a vacuum. The article was dried and calcined atabout 500° C. for about 1 hour. The loading of CuCHA in the top layerwas 1.8 g/in³.

In-Situ Blend ASC:

Bi-layer formulations having in-situ fixed Pt-support blend with Cu-CHAbottom layer and an SCR top layer with various support materials for Ptwere prepared by the previously described procedure.

The bottom layers comprised 3.5 wt % Pt on the supports listed inTable 1. The loading of Pt, the support material and the CuCHA on thearticle was 3 g/ft³, 0.05 g/in³, and 0.9 g/in³, respectively.

A top layer was applied to the substrate coated with the bottom layerusing a second washcoat comprising a Cu-CHA, then the washcoat waspulled down the substrate using a vacuum. The article was dried andcalcined at about 500° C. for about 1 hour. The loading of CuCHA in thetop layer was 1.8 g/in³.

The prepared catalysts were tested under the following conditions:

-   -   Aging conditions: 650 C under 10% H₂O in air for 50 hours    -   Testing conditions: 1 min 1000 ppm NH₃ pulse in 10% 02, 4.5%        H₂O, 4.5% CO₂, balance N₂; at SV=120,000 h⁻¹

FIG. 9 summarizes the NH₃ slip, N₂O and NOx formation when various ASCsare exposed to one minute pulse of 1000 ppm NH₃. All catalysts haveequivalent Pt loading at 3 g/ft³ and CuCHA top layer at the sameloading. Comparing to reference ASC, all blend ASCs (both pre-fixedPt-zeolite and in-situ Pt-support formulations) showed clear advantagesin lower N₂O and NOx formation. However, the NH₃ conversion efficiencyis highly dependent on the choice of Pt support material. Comparing topre-fixed Pt-zeolite blend ASC, the in-situ blend ASCs with alumina,silica-alumina or silica-titania as Pt support all showed similar orimproved NH₃ conversion. Samples with pure siliceous materials (fumedsilica, silica gel, and siliceous zeolite) as Pt support, in general,have worst NH₃ conversion; with the only exception of nano-zeolite whichshowed highest NH₃ conversion activity among all blend ASCs tested.

Example 2

Reference ASC

A bi-layer formulation having a Pt on alumina bottom layer and an SCRtop layer was used as a reference example

A bottom layer was applied to a ceramic substrate using a washcoatcomprising 0.17 wt % Pt on a blend of alumina and bare zeolite. Thewashcoat was applied to a ceramic substrate, then the washcoat waspulled down the substrate using a vacuum. The article was dried andcalcined at about 500° C. for about 1 hour. The loading of Pt on thearticle was 3 g/ft³.

A top layer was applied to the substrate coated with the bottom layerusing a second washcoat comprising a Cu-CHA, then the washcoat waspulled down the substrate using a vacuum. The article was dried andcalcined at about 500° C. for about 0.5 hour. The loading of CuCHA inthe top layer was 1.8 g/in³.

Pt-Zeolite Blend ASC:

A bottom layer was applied to a ceramic substrate using a washcoatcomprising a blend of 3.5 wt % Pt on a ZSM-5 (MFI framework withSAR=400) and one of the following: Cu-CHA, Cu-AEI, MnCu-CHA, or MnCuAEI.The washcoat was applied to a ceramic substrate, then the washcoat waspulled down the substrate using a vacuum. The article was dried andcalcined at about 500° C. for about 0.5 hour. The loading of Pt and theSCR on the article was 3 g/ft³, 0.045 g/in³, and 0.9 g/in³,respectively.

A top layer was applied to the substrate coated with the bottom layerusing a second washcoat comprising a Cu-CHA, then the washcoat waspulled down the substrate to a distance of about 50% of the length ofthe substrate using a vacuum. The article was dried and calcined atabout 500° C. for about 0.5 hour. The loading of CuCHA in the top layerwas 1.8 g/in³.

The formulations were labeled as follows:

-   -   ASC-1: Pt.Z+Cu.CHA blend bottom layer    -   ASC-2: Pt.Z+Cu.AEI blend bottom layer    -   ASC-3: Pt.Z+MnCu.CHA blend bottom layer    -   ASC-4: Pt.Z+MnCu.AEI blend bottom layer

The prepared catalysts were tested under the following conditions:

-   -   Aging conditions: 650 C under 10% H₂O in air for 50 hours    -   Testing conditions: 1 min 1000 ppm NH₃ pulse in 10% 02, 4.5%        H₂O, 4.5% CO₂, balance N₂; at SV=120,000 h⁻¹

As shown in FIG. 10, comparing Pt-zeolite blend ASCs with eitherCu.zeolite or MnCu.zeolite, the catalysts with MnCu.zeolite generallyshowed higher NH₃ conversions, and are comparable or better than theReference ASC. The N₂O formation on the blend ASCs with MnCu.zeolite issignificantly lower than the Reference ASC. In terms of NOx re-make, allPt-zeolite blend ASCs showed comparable results that is much lower thanthe Reference ASC. In summary, the CuMn.zeolites provide an advantage ofimproved NH₃ conversion while maintaining the benefits associated withthe Cu-zeolite for N₂O formation and NOx re-make. In addition, it showspromises in tuning the catalyst activity versus selectivity by adjustingthe Mn and Cu loadings and/or ratios.

1. A catalytic article comprising a substrate having an inlet and anoutlet; a first coating comprising a blend of: (1) platinum on asupport, and (2) a first SCR catalyst; and a second coating comprising asecond SCR catalyst; wherein the support comprises at least one of amolecular sieve or a SiO₂-Al₂O₃ mixed oxide, and wherein the first SCRcatalyst comprises a Cu- and Mn-exchanged molecular sieve.
 2. Thecatalytic article of claim 1, wherein the first SCR catalyst molecularsieve comprises a small pore molecular sieve.
 3. The catalytic articleof claim 1, wherein the first SCR catalyst molecular sieve comprisesAEI, CHA, or combinations thereof.
 4. The catalytic article of claim 1,wherein the first SCR catalyst molecular sieve is essentially free ofany transition metals beyond the Cu and Mn.
 5. The catalytic article ofclaim 1, wherein the first SCR catalyst molecular sieve comprises Cu andMn in a combined amount of about 0.10 to about 10% by weight of the Cu-and Mn-exchanged molecular sieve.
 6. The catalytic article of claim 1,wherein the first SCR catalyst molecular sieve comprises Cu in an amountof about 0.05 to about 5% by weight of the Cu- and Mn-exchangedmolecular sieve.
 7. The catalytic article of claim 1, wherein the firstSCR catalyst molecular sieve comprises Mn in an amount of about 0.05 toabout 5% by weight of the Cu- and Mn-exchanged molecular sieve.
 8. Thecatalytic article of claim 1, wherein the first SCR catalyst molecularsieve comprises Cu and Mn in a weight ratio of about 0.1 to about
 50. 9.The catalytic article of claim 1, wherein the platinum is fixed on thesupport in solution.
 10. The catalytic article of claim 1, wherein thesupport comprises a SiO₂-Al₂O₃ mixed oxide.
 11. The catalytic article ofclaim 10, wherein SiO₂ is present in an amount of 1 wt % to about 70 wt% of the mixed oxide.
 12. The catalytic article of claim 1, wherein thesupport comprises a molecular sieve.
 13. The catalytic article of claim12, wherein the molecular sieve comprises an external surface area of atleast 50 m²/g.
 14. The catalytic article of claim 12, wherein themolecular sieve is selected from the group of Framework Types consistingof CHA, LEV, AEI, AFX, ERI, SFW, KFI, DDR, ITE, BEA, MFI and FER. 15.The catalytic article of claim 1, wherein the platinum is present in anamount of 0.01-0.3 wt. % relative to the weight of the support ofplatinum+the weight of platinum+the weight of the first SCR catalyst inthe blend.
 16. The catalytic article of claim 1, wherein a weight ratioof the first SCR catalyst to platinum on the support is in the range of0:1 to 300:1 based on the weight of these components.
 17. The catalyticarticle of claim 1, where the blend further comprises at least one ofpalladium (Pd), gold (Au) silver (Ag), ruthenium (Ru) or rhodium (Rh).18. The catalytic article of claim 1, where the second SCR catalystcomprises a small pore molecular sieve selected from the group ofFramework Types consisting of CHA, LEV, AEI, AFX, ERI, SFW, KFI, DDR,and ITE.
 19. The catalytic article of claim 1, wherein the second SCRcatalyst comprises promoted-Ce—Zr or promoted-MnO₂.
 20. An exhaustsystem comprising the catalytic article of claim 1 and a means forintroducing a reductant upstream of the catalytic article.